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US7375150B2 - Anti-static composition and method for production thereof - Google Patents

Anti-static composition and method for production thereof Download PDF

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Publication number
US7375150B2
US7375150B2 US10/485,150 US48515004A US7375150B2 US 7375150 B2 US7375150 B2 US 7375150B2 US 48515004 A US48515004 A US 48515004A US 7375150 B2 US7375150 B2 US 7375150B2
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lithium
group
compound
alkylene
trifluoromethanesulfonyl
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US20040175573A1 (en
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Noriaki Fujihana
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Sanko Chemical Industry Co Ltd
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Sanko Chemical Industry Co Ltd
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Priority claimed from JP2001229137A external-priority patent/JP3766616B2/ja
Priority claimed from JP2001262201A external-priority patent/JP3766619B2/ja
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Assigned to SANKO CHEMICAL INDUSTRY CO., LTD. reassignment SANKO CHEMICAL INDUSTRY CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FUJIHANA, NORIAKI
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0075—Antistatics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/43—Compounds containing sulfur bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S524/91—Antistatic compositions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Definitions

  • the present invention relates to an antistatic composition excellent in electric resistivity, and to a method for producing the composition.
  • Known methods for imparting antistatic properties to resin include coating of an antistatic agent such as a surface active agent on the resin surface, and mixing of an antistatic agent into resin.
  • the method for coating an antistatic agent on the resin surface has the problem of lacking in practical usability as an antistatic resin with persistency because antistatic properties decrease significantly after a long period.
  • the problem with the method for mixing an antistatic agent into resin is that because of poor compatibility between antistatic agents and resin, the antistatic agent bleeds out on the surface of the molding, thus decreasing an antistatic effect.
  • Japanese Unexamined Patent Publication Nos. 64-9258 and 2-255852 aiming to overcome the problems of poor compatibility between antistatic agents and resin and of their poor dispersivility in vinyl chloride resin, disclose antistatic agents that utilize perchlorate such as ammonium perchlorate and lithium perchlorate.
  • perchlorate such as ammonium perchlorate and lithium perchlorate.
  • an antistatic composition that contains polyamide resin, polyether esteramide resin, aliphatic polyester, polylactic resin, thermoplastic elastomer and unvulcanized rubber, and alkali metal salt or alkaline earth metal salt is proposed (International Publication No. WO 01/79354A1).
  • the above perchlorate however, has the problem of impairing the thermo stability of vinyl chloride.
  • hydrophilic resin As a method for imparting electric resistivity to polyolefin resin, a method for adding hydrophilic resin is proposed (by, e.g., Japanese Unexamined Patent Publication Nos. 4-198308 and 7-126446).
  • This method requires the hydrophilic resin to be added at more than 10 percent by weight of the polyolefin resin in order for the resin to exhibit practically sufficient antistatic properties.
  • This presents the problem of impairing the physical properties of the substrate resin; for example, the strength of a molding decreases.
  • moisture on the resin surface decreases and so does antistatic properties resulting from moisture, presenting the problem of significantly impairing antistatic properties.
  • Japanese Unexamined Patent Publication No. 9-227743 discloses a transparent antistatic composition in which vinyl chloride resin, plasticizer, and lithium bis(trifluoromethanesulfonyl)imide are blended.
  • the blended amount of the lithium bis(trifluoromethanesulfonyl)imide is large with respect to the vinyl chloride resin, and this deteriorates thermo stability; when heated at 120° C. for 30 minutes, the composition becomes blackish brown, thus presenting the problem of losing transparency and antistatic properties.
  • an antistatic composition comprising: at least one compound selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide and lithium tris(trifluoromethanesulfonyl)methide; and polyurethane.
  • the polyurethane according to the present invention is excellent in, as well as antistatic properties, thermal resistance stability, is free from dependence on environment and the problem of bleeding out, and can be easily colored.
  • the at least one compound selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide and lithium tris(trifluoromethanesulfonyl)methide may be added at 0.01 to 20 percent by weight of the polyurethane material.
  • the ratio of the added compound is less than 0.01 percent by weight, antistatic properties are not exhibited sufficiently. On the other hand, if the ratio of the added compound exceeds 20 percent by weight, the effect to impart antistatic properties to the polyurethane becomes saturated, presenting the problem of causing cost increase.
  • the antistatic polyurethane according to the present invention may be produced as follows. When producing the polyurethane by the reaction of polyol having at least two activated hydrogen atoms with isocyanate, the at least one compound selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide and lithium tris(trifluoromethanesulfonyl)methide is added.
  • the adding of the at least one compound selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide and lithium tris(trifluoromethanesulfonyl)methide may be such that the compound is dissolved in the polyol. Since a compound that is able to impart antistatic properties is dissolved in the polyol, it is possible to produce polyurethane with uniform antistatic properties.
  • a solution in which the at least one compound selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide and lithium tris(trifluoromethanesulfonyl)methide is dissolved in water or an organic solvent at 0.1 to 90 percent by weight thereof may be added in the polyol.
  • polyurethane with uniform antistatic properties by dissolving the compound in a solvent that is capable of dissolving it. Note that if the dissolved concentration is less than 0.1 percent by weight, the antistatic properties of the obtained polyurethane may not be uniform. On the other hand, if the dissolved concentration exceeds 90 percent by weight, there arises the problem of causing cost increase.
  • an antistatic composition comprising: (A) at least one substance selected from the group consisting of a compound including moiety of an ether bond and/or moiety of an ester bond, and (co-)polymer including moiety of an ether bond; and (3) an anion adsorption processing substance obtained by processing alkali metal salt or alkaline earth metal salt by treating a compound having anionic adsorbability.
  • the compound including moiety of an ether bond and/or an ester bond may be a compound (C) including a group represented by the following general formula (1): —O(AO) n — (1)
  • A represents an alkylene group of 2 to 4 carbons and n represents an integer of 1 to 7.
  • the (co-)polymer including moiety of an ether bond may be at least one (co-)polymer selected from the group consisting of polyalkylene oxide resin and polyurethane resin.
  • the metal salt may be at least one lithium salt selected from the group consisting of lithium perchloride, trifluoromethanesulfonic acid lithium, lithium bis(trifluoromethanesulfonyl)imide, and lithium tris(trifluoromethanesulfonyl)methide.
  • the above lithium salt imparts excellent antistatic properties to resin.
  • the compound having anionic adsorbability may be at least one selected from the group consisting of synthetic hydrotalcite composed of magnesium and aluminum in major proportion, and an anion exchanger. Since a compound having anionic adsorbability adsorbs anions originating from metal salt, there is no corrosion, contamination, or rust on the metal surface.
  • the antistatic composition according to the present invention group can be produced by adding alkali metal salt or alkaline earth metal salt in at least one selected from the group consisting of a compound including moiety of an ether bond and/or moiety of an ester bond, and (co-)polymer including moiety of an ether bond, and by further adding a compound having anionic adsorbability.
  • the antistatic composition according to the present invention group by adding alkali metal salt or alkaline earth metal salt and a compound having anionic adsorbability in at least one selected from the group consisting of a compound including moiety of an ether bond and/or moiety of an ester bond, and (co-)polymer including moiety of an ether bond
  • an antistatic composition for a coating material comprising at least one compound selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide, lithium tris(trifluoromethanesulfonyl)methide, and trifluoromethanesulfonic acid lithium.
  • the at least one compound selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide, lithium tris(trifluoromethanesulfonyl)methide, and trifluoromethanesulfonic acid lithium may be included at 0.05 to 10.0 parts by weight of 100 parts by weight of a coating layer forming component included in the antistatic composition for a coating material.
  • the ratio of the added lithium salt is less than 0.05 part by weight, antistatic properties are not exhibited sufficiently. On the other hand, if the ratio of the added lithium salt exceeds 10.0 parts by weight, the effect to impart antistatic properties becomes saturated, presenting the problem of causing cost increase.
  • coating-layer forming component used in the present specification denotes resin composing the composition of the present invention and pigment, if desired, added in the composition.
  • the antistatic composition for a coating material according to the present invention group can be produced by dissolving at least one compound selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide, lithium tris(trifluoromethanesulfonyl)methide, and trifluoromethanesulfonic acid lithium in water, organic solvent, polymerizable monomer, prepolymer, or oligomer, and by adding the solution in a composition for a coating material.
  • the above lithium compounds are dissolved in any of the above solvents. Therefore, in producing the composition for a coating material, a solution in which uniform dissolution is realized is added, making it possible to obtain a composition for a coating material capable of imparting uniform antistatic properties. In addition, since heating is not necessary when dissolving the compound in the polymerizable monomer or the like, polymerization does not start at the time of preparation. Furthermore, the lithium compounds do not give off heat when dissolved in alcohol or an ether solvent.
  • the surface coat layer may have antistatic properties.
  • Methods for imparting antistatic properties to a molding of synthetic resin include a method for forming a molding from antistatic resin.
  • the place where the occurrence of electrostatic becomes a problem is the surface of an object. That is, not necessarily the entire molding is made of an antistatic substance. Therefore, as in the present invention, it is possible to easily impart antistatic properties to a molding by forming an antistatic surface coat layer on the surface of the molding.
  • the use of the antistatic resin composition for a coating material of the present invention realizes antistatic moldings and antistatic films or antistatic sheets, when the composition is coated on various moldings and films or sheets.
  • These can be utilized as, for example, carrier tapes for electronic parts such as ICs, condensers, transistors, or LSIs, or as containers called carrier trays.
  • the surface coat layer can be transparent or have any colors.
  • an antistatic composition comprising a combination of a compound (D), lithium salt (E), and a compound (F), the compound (D) being at least one compound selected from the group consisting of alkyl amide or an alkylene oxide adduct of alkylene amide represented by the following formula (2), and alkyl amine or an alkylene oxide adduct of alkylene amine represented by the following formula (3), the lithium salt (E) being at least one lithium salt selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide, lithium tris(trifluoromethanesulfonyl)methide, and trifluoromethanesulfonic acid lithium, and the compound (F) being at least one compound selected from the group consisting of polymerizable monomer, prepolymer, oligomer, and polymer:
  • R1 represents an alkyl group, an alkylene group, or an oxyalkylene group
  • R2 and R3 represent oxyalkylene groups that may be identical or different
  • x represents 0 or an integer of 2 to 50
  • y represents an integer of 2 to 50
  • R1 represents an alkyl group, an alkylene group, or an oxyalkylene group
  • R2 and R3 represent oxyalkylene groups that may be identical or different
  • x represents 0 or an integer of 2 to 50
  • y represents an integer of 2 to 50.
  • antistatic properties are exhibited by the at least one compound (D) selected from the group consisting of alkyl amide or an alkylene oxide adduct of alkylene amide represented by the above formula (2), and alkyl amine or an alkylene oxide adduct of alkylene amine represented by the above formula (3), and the at least one lithium salt (E) selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide, lithium tris(trifluoromethanesulfonyl)methide, and trifluoromethanesulfonic acid lithium, based on the function of each of the compound and the lithium salt. Therefore, it is possible to obtain an antistatic composition that is excellent in heat stability, is free from bleeding-out, is independent of humidity, has immediate effectiveness, and has persistent and excellent antistatic properties.
  • alkyl amide or an alkylene oxide adduct of alkylene amide, or of alkyl amine or an alkylene oxide adduct of alkylene amine makes it possible for lithium ions in the lithium compound to move within the molding, upon application of a voltage.
  • an ionic conduction passage is formed by the oxyalkylene group contained in alkyl amide or an alkylene oxide adduct of alkylene amide, or in alkyl amine or an alkylene oxide adduct of alkylene amine.
  • the lithium ions can move within the molding. This results in an increase in the ionic conductivity of the composition so that an electric antistatic effect is exhibited.
  • an antistatic composition excellent in immediate effectiveness is obtained.
  • alkyl amide or an alkylene oxide adduct of alkylene amide, or alkyl amine or an alkylene oxide adduct of alkylene amine represented by the above formula (3) exhibits an electric antistatic effect.
  • the lithium salt exhibits an electric antistatic effect.
  • an antistatic composition that exhibits an electric antistatic effect that is independent of humidity is obtained.
  • alkyl amide or an alkylene oxide adduct of alkylene amide, or alkyl amine or an alkylene oxide adduct of alkylene amine forms a thin film on a molding without bleeding out and exhibits an electric antistatic effect. Even if the thin film is removed because of an atmosphere of low humidity or by washing, these substances exude gradually out of the molding to form another thin film. This makes it possible to maintain excellent antistatic properties.
  • Alkyl amide or an alkylene oxide adduct of alkylene amide, or alkyl amine or an alkylene oxide adduct of alkylene amine, and the above lithium salt are transparent, making it possible to obtain a transparent antistatic composition.
  • the antistatic composition of the present invention group exhibits antistatic properties because of alkyl amide or an alkylene oxide adduct of alkylene amide, or alkyl amine or an alkylene oxide adduct of alkylene amine, and the lithium salt. This results in a decrease in the amount of the lithium salt blended in the composition, making it possible to obtain an antistatic composition that is excellent in thermo stability, transparency, and antistatic properties.
  • alkyl amide or an alkylene oxide adduct of alkylene amide represented by the above formula (2) may be polyoxyethylene alkyl amide, polyoxyethylene alkylene amide, polyoxypropylene alkyl amide, or polyoxypropylene alkylene amide
  • alkyl amine or an alkylene oxide adduct of alkylene amine represented by the above formula (3) may be polyoxyethylene alkyl amine, polyoxyethylene alkylene amine, polyoxypropylene alkyl amine, or polyoxypropylene alkylene amine.
  • the lithium salt (E) may be blended at 0.1 to 50 percent by weight of the at least one compound (D) selected from the group consisting of alkyl amide or an alkylene oxide adduct of alkylene amide represented by the above formula (2), and alkyl amine or an alkylene oxide adduct of alkylene amine represented by the above formula (3).
  • the ratio of the added lithium salt is less than 0.05 part by weight, antistatic properties begin to depend on humidity and may not be exhibited sufficiently under an atmosphere of low humidity. On the other hand, if the ratio of the added lithium salt exceeds 5.0 parts by weight, the effect to impart antistatic properties becomes saturated, presenting the problem of causing cost increase.
  • a total (D+E) of the compound (D) and the lithium salt (E) may be included at 0.05 to 10.0 parts by weight of 100 parts by weight of the resin compound (F) of the resin, the compound (D) being at least one compound selected from the group consisting of alkyl amide or an alkylene oxide adduct of alkylene amide represented by the above formula (2), and alkyl amine or an alkylene oxide adduct of alkylene amine represented by the above formula (3).
  • the mixture ratio of the antistatic agents is less than 0.05 part by weight, antistatic properties may not be exhibited sufficiently because of the small amount of the mixture. On the other hand, if the mixture ratio exceeds 10.0 parts by weight, the effect to impart antistatic properties becomes saturated, presenting the problem of causing cost increase.
  • the antistatic composition according to the present invention group can be produced by dissolving the lithium salt (E) in the compound (D) and by adding the solution in the compound (F), the lithium salt (E) being at least one lithium salt selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide, lithium tris(trifluoromethanesulfonyl)methide, and trifluoromethanesulfonic acid lithium, the compound (D) being at least one compound selected from the group consisting of alkyl amide or an alkylene oxide adduct of alkylene amide represented by the above formula (2), and alkyl amine or an alkylene oxide adduct of alkylene amine represented by the above formula (3), and the compound (F) being at least one compound selected from the group consisting of polymerizable monomer, prepolymer, oligomer, and polymer.
  • the lithium salt (E) being at least one lithium salt selected from the group consisting of lithium bis(trifluorome
  • the above lithium compound dissolves in the at least one compound (D) selected from the group consisting of alkyl amide or an alkylene oxide adduct of alkylene amide represented by the above formula (2), and alkyl amine or an alkylene oxide adduct of alkylene amine represented by the above formula (3). Therefore, the two antistatic substances are uniformly mixed. These uniformly mixed agents are added in the compound (F) selected from the group consisting of polymerizable monomer, prepolymer, oligomer, and polymer, making it possible to obtain an antistatic composition in which the two antistatic agents are uniformly dispersed.
  • the material components and methods for obtaining polyurethane used in the present invention are those known in the art, except those for obtaining the at least one compound selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide and lithium tris(trifluoromethanesulfonyl)methide.
  • Polyurethane is generally made by the reaction of diisocyanate and polyol.
  • the polyol used in the present invention should have at least two activated hydrogen atoms in the molecules thereof.
  • examples of such polyol include polyether polyol such as ethyleneoxide adducts and propyleneoxide adducts such as polyprene glycol, glycerol, trimethylol propane, and sorbitol; polyester polyol obtained by the reaction of acid such as adipic acid, succinic acid, maleic acid, and phthalic acid, with glycol such as ethylene glycol and butylene glycol; and polybutadiene polyol.
  • low-molecular polyol examples include 1,4-butanediol, ethylene glycol, propylene glycol, butylene glycol, and diethylene glycol.
  • polyether polyol, polyether polyol, and polytetramethylene ether glycol are preferable.
  • Examples of the isocyanate used in the present invention include, for example, tolylene diisocyanate, diphenylenemethane diisocyanate, hexamethylene diisocyanate, and prepolymer whose end has the above isocyanate.
  • catalyst e.g., amine compounds, quaternary ammonium salt compounds, polymer containing a quaternary ammonium base, or organometallic compounds may be added.
  • pigment may be added.
  • the mixture of pigment makes it easier to color the obtained antistatic polyurethane.
  • examples of usable pigment include inorganic pigment such as talc, titanium oxide, red iron oxide, clay, silica white, and calcium carbonate, and organic pigment such as azo pigment, phthalocyane pigment, and carbon black pigment.
  • the antistatic composition according to the present invention can be produced as follows.
  • polyurethane is produced by reacting polyol having at least two activated hydrogen atoms with isocyanate, the at least one compound selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide and lithium tris(trifluoromethanesulfonyl)methide is added.
  • the above compound may be added by dissolving the compound in the polyol.
  • the polyol capable of dissolving the above compound include, for example, low-molecular polyol such as monoethylene glycol, diethylene glycol, and 1,4-butanediol; polyether polyol and polyester polyol.
  • another polyol may be contained in addition to the above polyol that dissolves the above compound.
  • the solution to be added is preferably that in which at least one compound selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide and lithium tris(trifluoromethanesulfonyl)methide is dissolved at 0.1 to 90 percent by weight of the polyol having at least two activated hydrogen atoms.
  • the at least one compound selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide and lithium tris(trifluoromethanesulfonyl)methide may be added at 0.01 to 20 percent by weight of the polyurethane material, as mentioned above.
  • the antistatic polyurethane obtained in the present invention can be used for polyurethane foam of hard foam and soft foam; crosslinking or thermoplastic polyurethane elastomer; reactive injection molding polyurethane; synthetic fiber formed of a long-chain polymeric substance having 85 percent by weight of segmented polyurethane; and polyurethane coating material, all of which requiring high antistatic properties.
  • lithium imide denotes “lithium bis (trifluoromethanesulfonyl)imide
  • lithium methane denotes “lithium tris(trifluoromethanesulfonyl)methide.”
  • a coating material was prepared by mixing 150 parts hydrogenated 1,2-polybutadiene polyol (GI-1000, available from Mitsubishi Chemical Corporation), 65 parts trimethylol propane adduct (Takenate D-140N, available from Takeda Chemical Industries, Ltd.) of isophorone diisocyanate, 26 parts caprolactam adduct O405-80T, available from Asahi Chemical Industry Co., Ltd.) of hexamethylene diisocyanate, 10 parts polyethylene methacrylate copolymer (Reox AS-170, available from Dai-Ichi Kogyo Seiyaku Co., Ltd.) containing a quaternary ammonium base, 10 parts lithium imide, and 65 parts mixture solvent of toluene-methanol (70:30).
  • This coating material was applied on a rubber sheet of 1 mm thick by a spray method to form a surface coat layer of 30 ⁇ m thick. This surface coat layer was heated and dried for one hour at 120° C. and thus the film was cured. Thus, a covering layer A6 was prepared.
  • a mixture solution was prepared by mixing 25 parts sorbitol polyol (hydroxyl group (OHV): 450) in which 4 percent by weight lithium imide was dissolved, 75 parts pentaery thritol polyol (hydroxyl group (OHV): 450), 0.15 part pentamethyl diethylenetriamine, 1.5 parts silicone surface active agent, and 15 parts HCFC-141b.
  • sorbitol polyol hydroxyl group (OHV): 450
  • pentaery thritol polyol hydroxyl group (OHV): 450
  • 0.15 part pentamethyl diethylenetriamine 1.5 parts
  • silicone surface active agent 1.5 parts
  • the 1,4-dimethylol benzene was that in which 50 percent by weight lithium imide was dissolved.
  • This mixture was heated for six hours at 120° C. Thus, thermoplastic elastomer was obtained.
  • the obtained elastomer was cut into a pellet-like shape of about 5 mm in diameter. Thus cut elastomer was subjected to press working. Thus, a sheet-like specimen A8 of about 5 mm thick was obtained.
  • a plate-like specimen X1 was prepared in the same manner as Example 1-1 except that 8 parts ethylene glycol in which 5 percent by weight n-lauryl trimethyl ammonium chloride was dissolved instead of lithium imide was added.
  • Film-like transparent resin was obtained in the same manner as Example 1-4 except that propylene glycol polyether polyol without lithium imide dissolved therein was used. On the surface of this film, methanol in which 10 percent by weight 2-ethylhexyl ammonium nitrate was dissolved was applied by spray and dried Thus, film-like transparent resin X2 was obtained.
  • a plate-like specimen X3 was prepared in the same manner as Example 1-1 except that 8 parts ethylene glycol in which 5 percent by weight lithium perchlorate was dissolved instead of lithium imide was added.
  • lithium perchlorate instead of lithium imide as in Example 1-7, was meant to be dissolved in sorbitol polyol, it wasn't dissolved, failing to obtain a hard polyurethane foam.
  • Example A1 to A8 and Comparative Examples X1 to X3 were measured, the results of which are listed in Table 1.
  • Examples A1, A4, and Comparative Example X2 were left to stand under a stream of water for 30 minutes and then dried, after which their surface resistivity was measured again. The results are also listed in Table 1.
  • the measuring of the strength retention rate was performed after an accelarated wet-heat test under a condition of high temperature and humidity, i.e., at a temperature of 80° C. and a relative humidity of 95 percent.
  • Table 1 shows that the surface resistivity of Examples A1 to A4, A6 to A8, and Comparative Example X2 were lower than those of Comparative Examples X1 and X2.
  • the volume resistivity of Example A5 was also low.
  • the surface resistivity of the article of the present Example was kept low even after the underwater test. As a result, it has been found that antistatic properties are retained.
  • Example A1 and Comparative Example X3 it has been found that the present invention is excellent in a strength retention rate after the accelarated wet-heat test.
  • a component (A) used in the present invention is at least one selected from the group consisting of a compound including moiety of an ether bond and/or moiety of an ester bond and (co-)polymer including moiety of an ether bond. Such compound improves the solubility of metal salt used for a component (B) and stabilizes the metal salt in the composition of the present invention group.
  • the compound including moiety of an ether bond and/or moiety of an ester bond include a compound (C) including a group represented by the following general formula (1): —O(AO) n — (1)
  • A represents an alkylene group of 2 to 4 carbons and n represents an integer of 1 to 7.
  • the above compound (A) increases solubility and dissociation stability in a composition of the metal salt in the composition of the present invention group.
  • the above compound (C) can be produced by a common production method of an ester compound using raw material of a hydroxyl compound obtained by adding 1 to 7 moles of alkylene oxide with 2 to 4 carbons and dibasic acid in 1 mole of branched aliphatic alcohol.
  • the hydroxyl compound that can be used is not particularly limited; however, examples thereof include, for example, hydroxyl compounds in which 1 to 7 moles of ethylene oxide, 1 to 4 moles of propylene oxide, or 1 to 3 moles of butylene oxide is added in 1 mole of propanol; hydroxyl compounds in which 1 to 6 moles of ethylene oxide or 1 to 3 moles of propylene oxide is added in 1 mole of butanol; hydroxyl compounds in which 1 to 2 moles of ethylene oxide is added in 1 mole of hexanol; hydroxyl compounds in which 1 to 5 moles of ethylene oxide, 1 to 3 moles of propylene oxide, or 1 to 2 moles of butylene oxide is added in 1 mole of pentanol; hydroxyl compounds in which 1 to 5 moles of ethylene oxide, 1 to 2 moles of propylene oxide, or 1 to 3 moles of butylene oxide is added in 1 mole of octanol; and hydroxyl compounds in which 1 to 4
  • Preferable hydroxyl compounds among the foregoing hydroxyl compounds are 2-(2-butoxyethoxy)ethanol in which 2 moles of ethylene oxide is added in 1 mole of butanol, and 2-butoxy ethanol in which 1 mole of ethylene oxide is added in 1 mole of butanol. These are suitable for processing a composition.
  • dibasic acid examples include carboxylic acid such as adipic acid, sebacic acid, phthalic acid, and succinic acid, and carboxylic acid anhydride thereof.
  • Examples of preferable compound (C) include bis[2-(2-butoxyethoxy)ethyl]adipate, bis(2-butoxyethyl)phthalates, and the like.
  • Examples of the compound including moiety of an ether bond and/or an ester bond include, for example, polymerizable monomer, prepolymer, and oligomer that include moiety of an ether bond and/or moiety of an ester bond.
  • Specific examples of the polymerizable monomer, prepolymer, and oligomer include those of polyethylene glycol di(meth)acrylate such as ethylene glycol di(meth)acrylate, diethylene glycol(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylol propane ethoxy(meth)acrylate, trimethylol propane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and ethoxy diethylene glycol(meth)acrylate, and polypropylene glycol(meth)acrylate.
  • examples of the compound include polypropylene glycol, polyether polyol such as polymer polyol polytetramethylene glycol, adipate polyol, phthalate polyol, polycaprolactam polyol, polyester polyol such as polycarbonate polyol, polybutadiene polyol, and acrylic polyol.
  • polyether polyol such as polymer polyol polytetramethylene glycol, adipate polyol, phthalate polyol, polycaprolactam polyol
  • polyester polyol such as polycarbonate polyol, polybutadiene polyol, and acrylic polyol.
  • the compound including moiety of an ether bond and/or moiety of an ester bond can be used as it is, or in the form of a solution in which the compound is dissolved in a solvent.
  • Examples of the (co-)polymer including moiety of an ether bond used in the present invention group include, for example, polyoxyethylene, polyoxypropylene, polyoxytetramethylene, polyalkylene oxide resin such as ethyleneoxide-propyleneoxide copolymer; polyethylene glycol-polyamide copolymer having a polyether segment; polyethylene glycol methacrylate copolymer; and polyurethane resin having a segment of polyethylene glycol, polypropylene glycol, polybutylene glycol, or the like. Polyalkylene oxide resin and polyurethane resin are preferred.
  • a component (B) is an anion adsorption processing substance obtained by processing alkali metal salt or alkaline earth metal salt by treating a compound having anionic adsorbability.
  • the alkali metal salt or alkaline earth metal salt used in the component (B) in the present invention group is composed of cations of alkali metal or alkaline earth metal and anions that are capable of ionic dissociation.
  • Examples of the alkali metal or alkaline earth metal include Li, Na, K, Mg, and Ca.
  • Preferable cations are Li + , Na + , and K + with a small ionic radius, and Li + is particularly preferable.
  • Examples of the anions that correspond to the cations of the alkali metal or alkaline earth metal include, for example, Cl ⁇ , Br ⁇ , F ⁇ , I ⁇ , NO 3 ⁇ , SCN ⁇ , ClO 4 ⁇ , CF 3 SO 3 ⁇ , BF 4 ⁇ , (CF 3 SO 2 ) 2 N ⁇ , and (CF 3 SO 2 ) 3 C ⁇ ,
  • Preferable anions are ClO 4 ⁇ , CF 3 SO 3 ⁇ , (CF 3 SO 2 ) 2 N ⁇ , and (CF 3 SO 2 ) 3 C ⁇
  • more preferable anions are CF 3 SO 3 ⁇ , (CF 3 SO 2 ) 2 N ⁇ , and (CF 3 SO 2 ) 3 C ⁇ .
  • the alkali metal salt or alkaline earth metal salt used in the present invention group is composed of the above cations and anions.
  • Examples of preferable alkali metal salt include lithium perchlorate LiClO 4 , sodium perchlorate NaClO 4 , magnesium perchlorate Mg(ClO 4 ) 2 , potassium perchlorate KClO 4 , trifluoromethanesulfonic acid lithium LiCF 3 SO 3 , lithium bis(trifluoromethanesulfonyl)imide Li (CF 3 SO 2 ) 2 N, potassium bis(trifluoromethanesulfonyl)imide K (CF 3 SO 2 )N, sodium bis(trifluoromethanesulfonyl)imide Na (CF 3 SO 2 ) 2 N, lithium tris(trifluoromethanesulfonyl)methide Li (CF 3 SO 2 ) 3 C, and sodium tris(trifluoromethanesulfonyl)methide Na
  • More preferable anions are lithium perchlorate, trifluoromethanesulfonic acid lithium bis(trifluoromethanesulfonyl)imide lithium, and lithium tris(trifluoromethanesulfonyl)methide.
  • Particularly preferable anions are trifluoromethanesulfonic acid lithium bis(trifluoromethanesulfonyl)imide lithium and lithium tris(trifluoromethanesulfonyl)methide.
  • the component (B) in the present invention group can be obtained by processing the above metal salt by treating a compound having anionic adsorbability.
  • known compound in the art are effective such as synthetic hydrotalcite composed of magnesium and aluminum in major proportion, (co)polymer with an Mg—Al, Sb, or Ca inorganic ion exchanger, and an anion exchanger group that is held in the three-dimensional reticulated structure of the (co-)polymer.
  • the compound having anionic adsorbability include, for example, synthetic hydrotalcite (brand name: Kyoward KW-2000 and Kyoward KW-1000, available from Kyowa Chemical Industry Co., Ltd.), synthetic adsorbent (brand name: Cue Fine 2000, available from Tomita Pharmaceutical Co., Ltd.), and anion exchanger resin (brand name: Diaion DCA11, available from Nippon Rensui Co.).
  • synthetic hydrotalcite brand name: Kyoward KW-2000 and Kyoward KW-1000, available from Kyowa Chemical Industry Co., Ltd.
  • synthetic adsorbent brand name: Cue Fine 2000, available from Tomita Pharmaceutical Co., Ltd.
  • anion exchanger resin brand name: Diaion DCA11, available from Nippon Rensui Co.
  • the added amount of the compound having anionic adsorbability is 0.01 to 5.0 chemical equivalent to 1 chemical equivalent of the metal salt. If the added amount is less than 0.01 chemical equivalent, the amount of anion adsorption is insufficient. On the other hand, if the added amount exceeds 5.0 chemical equivalent, an antistatic effect becomes saturated, which is economically disadvantageous.
  • the anion exchanger When using the anion exchanger as the compound having anionic adsorbability, the ion exchanger releases hydroxyl ions. Therefore, it is necessary to add a compound that captures the hydroxyl ions such as a carboxylic acid compound in order to remove the hydroxyl ions by means of neutralization.
  • the compound having anionic adsorbability may be removed by filtration or the like, or may be contained in the antistatic composition.
  • a method for processing the above metal salt by treating the compound having anionic adsorbability is not particularly limited; for example, the following methods may be employed
  • a processing method such that metal salt is dissolved in a compound including moiety of an ether bond and/or moiety of an ester bond or in a solution thereof, after which a compound having anionic adsorbability is added therein.
  • a processing method such that into a compound including moiety of an ether bond and/or moiety of an ester bond or into a solution thereof, a compound having anionic adsorbability is added in advance, after which metal salt is dissolved therein.
  • the antistatic composition according to the present invention group is produced in, for example, the following manner.
  • alkali metal salt or alkaline earth metal salt is dissolved in a compound including (A) moiety of an ether bond and/or moiety of an ester bond or in a solution thereof in order to obtain a mixture.
  • the dissolved metal salt should have a ratio of preferably 0.1 to 80 percent by weight, more preferably 0.5 to 50 percent by weight of a total of the compound including moiety of an ether bond and/or moiety of an ester bond and the metal salt.
  • the alkali metal salt or the alkaline earth metal salt is added and mixed uniformly at a ratio of preferably 0.1 to 50 percent by weight, more preferably 0.5 to 30 percent by weight of a total of the (co-)polymer including moiety of an ether bond and the metal salt in order to obtain a mixture.
  • the mixing may be conducted by heating and dissolving.
  • the amount of the metal salt is less than the above-specified range, a sufficient antistatic effect cannot be obtained. On the other hand, if the amount of the metal salt exceeds the above-specified range, almost no improvement in an antistatic effect can be seen, which is economically disadvantageous.
  • an antistatic composition according to the present invention group is obtained.
  • Conditions for the anion adsorption treatment when the (co-)polymer is not contained in the mixture are ordinarily 20 to 100° C. temperature and a period of 10 to 120 minutes, and preferably, 30 to 90° C. temperature and a period of 20 to 90 minutes.
  • the conditions vary depending on the kind of the (co-)polymer contained; ordinarily, the temperature is ⁇ 20 to 200° C. and the period is 1 to 60 minutes, and preferably, the temperature is ⁇ 10 to 180° C. and the period is 3 to 30 minutes. If the conditions are outside these ranges, anionic adsorbability may not be exhibited sufficiently or the copolymer may be degraded, which is not preferable.
  • the antistatic composition according to the present invention group may further contain at least one substance selected from the group consisting of thermoplastic resin, unvulcanized rubber, and thermoplastic elastomer.
  • part in each example respectively denote “part by weight,” “parts by weight,” and “percent by weight,” unless specifically noted otherwise.
  • the (co-)polymer used here include that corresponds to the component (A) and that does not correspond thereto, for convenience, it is assigned the symbol (d), and thus denoted a component (d).
  • c-1 bis[2-(2-butoxyethoxy)ethyl]adipate, available from Sanko Kagaku Kogyo Co., Ltd.;
  • c-2 bis(2-butoxyethyl)phthalate, available from Sanko Kagaku Kogyo Co., Ltd.;
  • c-3 polyethylene glycol dimethacrylate (number of oxymethylene units: 3), available from Mitsubishi Rayon Co., Ltd.;
  • c-4 propylene glycol polyether polyol (hydroxyl group (OHV): 56), brand name: Actcall MN-3050BM, available from Mitsui Takeda Chemicals, Inc.;
  • b′-1 synthetic hydrotalcite; anionic removal activation: 6.7 m chemical equivalent/g; brand name: Kyoward KW-2000, available from Kyowa Chemical Industry Co., Ltd.;
  • b′-2 synthetic hydrotalcite; anionic removal activation: 3.8 m chemical equivalent/g; brand name: Kyoward KW-1000, available from Kyowa Chemical Industry Co., Ltd.;
  • b′-3 synthetic adsorbent; anionic removal activation: 6.7 m chemical equivalent/g; brand name: Cue Fine 2000, available from Tomita Pharmaceutical Co., Ltd.;
  • b′-4 anion exchanger resin; anionic removal activation: 6.7 m chemical equivalent/g; brand name: Diaion DCA11, available from Nippon Rensui Co.;
  • d-2 ethyleneoxide-propyleneoxide copolymer, brand name: ZSN8030, available from Zeon Corporation; and
  • thermoplastic polyurethane resin brand name: Pandex T-1190, available from Dainippon Ink and Chemicals, Incorporated.
  • this solution was set at 60° C., and then b′-1: synthetic hydrotalcite (KW-2000) was added therein so that (b′-1) was 2 percent of the total of (c-1), (b-1), and (b′-1). Then, this solution was stirred at 60° C. for 60 minutes and filtered. Thus, a transparent liquid (antistatic composition) was obtained.
  • the volume resistivity of the obtained antistatic composition was 4.1 ⁇ 10 6 ⁇ cm.
  • the antistatic compositions (liquid) of Examples 2-1 to 2-4 obtained by anion adsorption treatment have been found to be good antistatic compositions with reduced volume resistivity, compared with the comparative composition of Comparative Example 2-1.
  • a metal piece (1 cm ⁇ 5 cm, 1 mm thick) was immersed in the antistatic composition (antistatic composition B2) obtained in Example 2-2 and was left to stand at 25° C. for 7 days, after which the occurrence of rust was visually inspected. No rust was found to have emerged.
  • Example 2-2 Five parts antistatic composition obtained in Example 2-2 was blended with 100 parts (d-1) nitrile rubber, and this mixture was kneaded and subjected to extrusion. Thus, a sheet was prepared. In extrusion, a sheet of 0.1 mm thick was prepared using a single extruder of 20 mm with the temperature of the cylinder set at 140 to 190° C., and using a T-die with a screw of 10 to 30 rpm. The surface resistivity of this sheet was 9.1 ⁇ 10 7 ⁇ /sq. The results are listed in Table 3.
  • Example 2-5 A sheet was prepared in the same manner as Example 2-5 except that no antistatic composition was added.
  • the surface resistivity of this sheet was 9 ⁇ 10 13 ⁇ /sq.
  • the results are listed in Table 3.
  • Example 2-6 A sheet was prepared in the same manner as Example 2-6 except that no synthetic hydrotalcite was added.
  • the surface resistivity of this sheet was 1 ⁇ 10 9 ⁇ cm. The results are listed in Table 3.
  • a transparent liquid was obtained in the same manner as Example 2-7 except that no anion adsorption treatment using (b′-1) synthetic hydrotalcite was performed.
  • a molding of cured resin was obtained in the same manner as Example 2-7.
  • the volume resistivity of the obtained molding was 2 ⁇ 10 9 ⁇ cm.
  • a transparent liquid was obtained in the same manner as Example 2-8 except that no anion adsorption treatment using (b′-1) synthetic hydrotalcite was performed.
  • a molding of soft urethane foam was obtained in the same manner as Example 2-8.
  • the volume resistivity of the obtained molding was 8 ⁇ 10 9 ⁇ cm.
  • any resin known in the art can be used insofaras it is usable for coating materials.
  • examples of such resin include non-reactive type resin for a coating material such as cellulosic derivative, nitrocellulose, acetylcellulose, acetylbutylcellulose, ethylcellulose, benzylcellulose, and the like; vinyl resin, vinyl chloride-vinyl acetate polymer resin, polyvinyl butyral resin, polybutene, polybutadiene, and the like; acrylic resin; polyvinyl acetal; saturated polyester resin; and fluoroplastic, polyvinyl fluoride, tetrafluoroethylene-hexafluoropropylene copolymer resin, tetrafluoroethylene-perfluoroalkylvinylether copolymer resin, and the like; and reactive type resin for a coating material such as alkyd resin; amino resin, but
  • the antistatic composition for a coating material according to the present invention group can be used in the form of any known coating material in the art such as non-solvent coating material, organic solvent coating material, high solid coating material, powdered coating material, aquerous emulsion coating material, cathodic electrodeposition coating material, or the like.
  • organic solvent that can be used for the antistatic composition for a coating material according to the present invention group
  • any known organic solvent in the art can be used.
  • organic solvent include alcohol such as methanol, ethanol, isopropanol, 1-butanol; 2-buthanol, 2-pentanol, cyclohexanol, 1-methylcyclohexanol, trans-2-methylcyclohexanol, cis-2-methylcyclohexanol, trans-3-methylcyclohexanol, cis-3-methylcyclohexanol, trans-4-methylcyclohexanol, and cis-4-methylcyclohexanol; ketone such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, and 4-methylcyclohexan
  • Examples of the polymerizable monomer, prepolymer, or oligomer that are used for the antistatic composition for a coating material according to the present invention group include any known polymerizable monomer, prepolymer, or oligomer in the art that compose a composition in the state of polymerizable monomer, prepolymer, or oligomer, and are polymerized to form a surface coat layer.
  • examples thereof include monofunctional acrylate such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, n-butyl(meth)acrylate, t-butyl(meth)acrylate, isobutyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isoamyl(meth)acrylate, isooctyl(meth)acrylate, decyl(meth)acrylate, isodecyl(meth)acrylate, n-nonyl(meth)acrylate, cyclohexyl(meth)acrylate, lauryl(meth)acrylate, stearyl(meth)acrylate, benzil(meth)acrylate, dicydopentanyl(meth)acrylate, 2-dicydopentenoxyethyl(meth)acrylate, tricyclodecanyl(meth)acrylate,
  • low-molecular polyhydric alcohol with at least three hydroxyl groups in the molecules thereof and with carbons of 3 to 16, and polyol in which the chain is extended by adding a lactone compound such as ⁇ -caprolactam to the low-molecular polyhydric alcohol can also be used here.
  • examples thereof include trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, ditrimethylolpropane, pentaerythitol, dipentaerythritol, glycerol, a mixture thereof, and an additive of them and a lactone compound such as ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -valerolactone, and ⁇ -butyrolactone.
  • Silicate oligomer is another example.
  • the antistatic composition for a coating material according to the present invention group is used as a non-solvent coating material, an organic solvent coating material, or a high solid type coating material, then at least one compound selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide, lithium tris(trifluoromethanesulfonyl)methide, and trifluoromethanesulfonic acid lithium is dissolved in any of an organic solvent, polymerizable monomer, prepolymer, or oligomer.
  • the antistatic composition for a coating material according to the present invention is produced.
  • the antistatic composition for a coating material When the antistatic composition for a coating material is used as an aquerous emulsion coating material, the above lithium compound is dissolved in water, thus producing the antistatic composition for a coating material according to the present invention.
  • the antistatic composition for a coating material When the antistatic composition for a coating material is used as a powdered coating material, the above lithium compound is dissolved in water, an organic solvent, or the like together with resin, and then the solvent is removed to powderize the compound. Thus, the antistatic composition for a coating material according to the present invention is produced.
  • the antistatic composition for a coating material according to the present invention group may be dried, set or cured by known methods in the art such as, depending on the kind of resin used, solvent volatilization, oxidation under room temperature, oxidation by warning, condensation, or polymerization in order to form a surface coat layer.
  • curing can be performed by radiation of an activation energy ray such as an ultraviolet ray, a visible ray, and an electron ray.
  • an activation energy ray such as an ultraviolet ray, a visible ray, and an electron ray.
  • photopolymerization initiator is preferably included in the composition.
  • the photopolymerization initiator that can be used may be any known photopolymerization initiator in the art. Specifically, examples thereof include benzophenone, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenylbenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, benzoin, benzoinmethyl ether, benzoinethyl ether, benzoinisopropyl ether, benzoinisobutyl ether, benzyldimethyl ketal, diethoxyacetophene, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 1-hydroxycyclohexylphenylketone, thioxantone, 2-chlorothioxantone, 2,4-dimethylthioxantone, 2-isopropylthioxantone, 2,4-diethylthioxantone,
  • auxiliaries for initiating photoreaction or photosensitizers may be used together with the photopolymerization initiator.
  • examples thereof include triethanolamine, diethanolamine, methyldiethanolamine, triisopropanolamine, 4,4′-diethylaminobenzophein, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, benzoic acid-2-dimethylaminoethyl, dibutylamine, triethylamine, triethylenetetramine, diethylaminoethyl(meth)acrylate, and tributylphosphine.
  • additives examples include dye, pigment, filler, silane coupling agent, adhesion modifier, stabilizer, leveling agent, antifoaming agent, anti-settling additive, lubricant, and rust preventive.
  • the thickness of the cured surface coat layer is 1 to 25 ⁇ m, preferably 3 to 15 ⁇ m, and particularly preferably 5 to 10 ⁇ m. If the surface coat layer is less than 1 ⁇ m thick, sufficient antistatic properties cannot be obtained. If the thickness of the surface coat layer exceeds 25 ⁇ m, adhesiveness decreases, which is not preferable.
  • lithium imide denotes “lithium bis(trifluoromethanesulfonyl)imide
  • lithium methide denotes lithium tris(trifluoromethanesulfonyl)methide
  • lithium triflate denotes “trifluoromethanesulfonic acid lithium.”
  • a composition for a coating material in the state of a solution of 2 percent by weight was prepared using 65 parts polyethylene glycol methacrylate (polymerization degree: 90, oxyethylene unit: 20) water soluble resin, 2 parts lithium imide, 7 parts water melamine resin, and 15 parts nonionic surface active agent (brand name: Nonion NS 208.5, available from NOF Corporation).
  • a melt-extrusion non-stretched sheet of polyethylene terephthalate (intrinsic viscosity: 0.65, orthochlorophenol, 35° C.) was stretched by a factor of 3.5, and then 10 g/m 2 of the composition for a coating material was applied to a single side of the film by a casting method.
  • the film was extended laterally by a factor of 3.8 (105° C.) and subjected to heating treatment (205° C.).
  • a transparent single-side-coated polyester film with 15 ⁇ m total thickness of the film and surface coat layer was obtained.
  • the surface resistivity of this film was 2 ⁇ 10 8 ⁇ /sq.
  • a single-side-coated polyester film of Comparative Example 3-1 was obtained in the same manner as Example 3-1 except that 2 parts lithium perchlorate was dissolved instead of lithium imide.
  • the surface resistivity of this film was 2 ⁇ 10 10 ⁇ /sq.
  • a transparent antistatic sheet with a conductive layer of 10 ⁇ m thick was obtained.
  • the surface resistivity of this sheet was 3 ⁇ 10 8 ⁇ /sq.
  • washed plates of copper and of aluminum were placed and left to stand for 7 days in an atmosphere of a relative humidity of 40 percent and of a temperature of 20° C., after which each of the plates were visually inspected. No rust was found to have emerged.
  • An antistatic sheet of Comparative Example 2 was obtained in the same manner as Example 3-2 except that 10 parts lithium perchlorate was dissolved instead of lithium methane. Note that when the lithium perchlorate was dissolved in methyl ethyl ketone, a remarkable amount of heat evolved. Because of this heat, the 10 parts lithium perchlorate was dissolved little by little with care in 260 parts methyl ethyl ketone, during which the lithium perchlorate was cooled by ice. The surface resistivity of this film was 1 ⁇ 10 10 ⁇ /sq.
  • a cured-resin-composition molding in Comparative Example 3 was obtained in the same manner as Example 1 except that 20 parts lithium perchlorate was added instead of lithium imide. There were fine particles found on the surface of the cured resin. The volume resistivity of this molding was 2 ⁇ 10 11 ⁇ cm.
  • a transparent polycarbonate resin plate of Comparative Example 4 with a cured surface coat layer of 8 ⁇ m thick was obtained in the same manner as Example 4 except that barium perchlorate was dissolved instead of lithium triflate.
  • the surface resistivity of this film was 2 ⁇ 10 10 ⁇ /sq.
  • Antistatic resin coating structure for a coating material of Comparative Example 3-5 was obtained in the same manner as Example 3-5 except that lithium perchlorate was dissolved instead of lithium imide.
  • the voltage damping resistance of this coating structure was measured when a voltage of 8 kV was applied. When voltage resistance was 3000 V, the half life was 10 seconds or more.
  • An electrolytic solution (A) made of 22 parts water-soluble epoxy resin, 1.8 parts diethylamine, 8 parts titanium white, 2.3 parts lithium imide, 1.5 parts basic silicate, and 33.6 parts water, and an electrolytic solution (13) made of 8.6 parts polyisocyanate and 22.2 parts cellosolve were prepared Then, the solutions (A) and (B) were blended and this mixture was applied on a steel plate that was for serving as a substrate and was provided with sufficient adhesion by water washing to a thickness of 30 ⁇ m by electrostatic coating (applied voltage: 60 kV). Then this product was subjected to baking for 20 minutes at 170° C. Thus, a white surface coat layer was formed. The surface resistivity of this film was 2 ⁇ 10 10 ⁇ /sq.
  • An electrolytic solution A of Comparative Example 3-6 was prepared in the same manner as Example 3-6 except that lithium perchlorate was dissolved instead of lithium imide. The generated electrolytic solution was not uniform because of precipitates.
  • Alkyl amide or an alkylene oxide adduct of alkylene amide and alkyl amine or an alkylene oxide adduct of alkylene amine are represented by the following formulae (2) and (3):
  • R1 represents an alkyl group, an alkylene group, or an oxyalkylene group
  • R2 and R3 represent oxyalkylene groups that may be identical or different
  • x represents 0 or an integer of 2 to 50
  • y represents an integer of 2 to 50
  • R1 represents an alkyl group, an alkylene group, or an oxyalkylene group
  • R2 and R3 represent oxyalkylene groups that may be identical or different
  • x represents 0 or an integer of 2 to 50
  • y represents an integer of 2 to 50.
  • the alkyl group or alkylene group represented by R1 includes a straight-chained or branched alkyl group or a straight-chained or branched alkylene group.
  • the number of carbons included in the alkyl group or alkylene group may be determined such that the molecules thereof are provided with hydrophilicity and hydrophobicity to an appropriate extent.
  • Examples of such alkyl group or alkylene group include preferably an alkyl group or alkylene group with 8 to 22 carbons, more preferably an alkyl group or alkylene group with 10 to 20 carbons, and particularly preferably an alkyl group or alkylene group with 12 to 18 carbons.
  • the oxyalkylene group include preferably an oxyalkylene group with 2 to 10 carbons, more preferably an oxyalkylene group with 2 to 6 carbons, and particularly preferably an oxyalkylene group with 2 to 4 carbons.
  • examples of such oxyalkylene group include oxyethylene and oxypropylene, and oxyethylene is preferable.
  • R1 and R2 may be identical to each other or different from each other.
  • x and y are identical to each other or different from each other, but they are preferably identical. If they are different, x can be 0.
  • alkyl amide or an alkylene oxide adduct of alkylene amide and alkyl amine or an alkylene oxide adduct of alkylene amine can be used alone or in a combination of two or more thereof.
  • polymerizable monomer prepolymer, oligomer, and polymer denote polymer material and polymer raw material thereof. Polymer material is ultimately used as a molding of resin or rubber.
  • any known resin in the art can be used.
  • resin include thermoplastic resin such as polyolefin resin, polyethylene, polypropylene, polybutene, EVA resin, EVOH resin, and the like; polystyrene resin, polystyrene, AS resin, ABS resin, AXS resin, and the like; polyamide resin, nylon 6, nylon 6, 6, nylon 6, 10, nylon 12, and the like; acetal resin; saturated polyester, polyethylene terephthalate, polybutylene terephthalate, poly 1,4-cyclohexyldimethylene terephthalate, wholly aromatic polyester, and the like; polycarbonate; acrylic resin; thermoplastic elastomer; vinyl chloride resin, vinyl chloride resin, vinylidene chloride resin, and the like; fluorocarbon resin, polyvinyl fluoride, tetrafluoroethylene-hexafluoropropylene copolymer resin, tetrafluoroethylene
  • thermoplastic resin such as polyolefin resin, polyethylene,
  • any known rubber in the art can be used.
  • examples of such rubber include natural rubber; isoprene rubber; butadiene rubber; styrene-butadiene rubber and SBR; butyl rubber; ethylene-propylene rubber, EPR, EPDR, EPDM; chloroprene rubber; acrylonitrile-butadiene rubber and NBR; chlorosulfonated polyethylene; epichlorohydrin rubber, CHR, and ECO; chlorinated polyethylene; silicone rubber; fluorinated rubber; urethane rubber; styrene-butadiene copolymer; and the like.
  • the above rubber can be used alone or in a combination of two or more thereof.
  • the above resin and rubber can be used in combination.
  • the antistatic composition according to the present invention is produced in, for example, the following manner.
  • At least one lithium salt (E) selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide, lithium tris(trifluoromethanesulfonyl)methide, and trifluoromethanesulfonic acid lithium is dissolved in at least one compound (D) selected from the group consisting of alkyl amide or an alkylene oxide adduct of alkylene amide represented by the following formula (2), and alkyl amine or an alkylene oxide adduct of alkylene amine represented by the following formula (3).
  • the lithium salt (E) is dissolved so that the lithium salt (E) is 0.1 to 50 percent by weight, preferably 0.5 to 30 percent by weight of the at least one compound (D) selected from the group consisting of alkyl amide or an alkylene oxide adduct of alkylene amide represented by the above formula (2), and alkyl amine or an alkylene oxide adduct of alkylene amine represented by the above formula (3).,
  • the mixture of the compound (D) and the lithium salt (E) is added in at least one compound (F) selected from the group consisting of polymerizable monomer, prepolymer, oligomer, and polymer.
  • a composition according to the present invention is obtained.
  • the mixture of the compound (D) and the lithium salt (E) is added so that the total (D+E) of the at least one compound selected from the group consisting of alkyl amide or an alkylene oxide adduct of alkylene amide represented by the above formula (2), and alkyl amine or an alkylene oxide adduct of alkylene amine represented by the above formula (3) and the lithium salt is included at 0.05 to 10.0 parts by weight, preferably 0.1 to 5.0 parts by weight, more preferably 0.25 to 2.0 parts by weight of 100 parts by weight of the compound (F), which is at least one compound selected from the group consisting of polymerizable monomer, prepolymer, oligomer, and polymer.
  • the compound (F) which is at least one compound selected from the group consisting of polymerizable monomer, prepolymer, oligomer, and polymer.
  • a method for producing the composition according to the present invention is not particularly limited; any known methods in the art can be employed.
  • dry blending can be performed using Henschel mixer, ribbon blender, super mixer, tumbler, or the like.
  • melt kneading can be performed using single screw or twin screw extruder, Banbury mixer, plastomill, Ko-kneader, roll, or the like.
  • the production of the composition can be performed in an atmosphere of inert gas such as nitrogen.
  • the shape of the obtained composition is not particularly limited; it may be in any forms such as powder, pellet, sheet, strand, and chip.
  • the composition may be in a solution liquid state in which the mixture of the compound (D) and the lithium salt (E) is added in the at least one compound (F) selected from the group consisting of polymerizable monomer, prepolymer, oligomer, and polymer, all of which are in a solution liquid state.
  • any known additive in the art can be added as necessary such as antioxidant, heat stabilizer, ultraviolet absorber, fire retardant, fire retardant auxiliary, coloring agent, pigment, antimicrobial and antifungal agent, light resistance agent, plasticizer, tackifier, dispersing agent, antifoaming agent, curing catalyst, curing agent, leveling agent, coupling agent, filler, vulcanizing agent, and vulcanization accelerator.
  • the antistatic composition obtained by the above production method can be formed into shape by any known forming methods in the art such as compression molding, transfer molding, laminated molding, injection molding, extrusion molding, blow molding, calendering, casting, pasting, powdering, reaction molding, thermoforming, blow molding, rotational molding, vacuum molding, cast molding, and gas-assisted molding.
  • the antistatic composition according to the present invention can be used as an antistatic coating material composition.
  • the molding according to the present invention can be widely applied to products that are required to maintain high antistatic properties over a long period.
  • examples of such products include vehicle parts, household electrical appliance parts, electronics device parts, manufacturing equipment of electronic material, information office equipment parts, communication equipment, housing members, optical machine parts, sundry goods, industrial material, wrapping material used in distribution, and the like.
  • the molding can be utilized as tires, hoses, films for wrapping, wrapping material, sealing material, gloves, synthetic leather, ICs, condensers, transistors, carrier tapes for electronic parts such as LSIs and containers called carrier trays.
  • the molding may have any colors.
  • the following table shows the kind and ratio of (D) and (E).
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Compound PP EPDM PS TPU PC (C) Mixture No. P-1 P-2 P-3 P-4 P-5 Added 0.25 0.5 1.0 0.5 0.25 mount (% by weight) Surface 2 ⁇ 10 8 2 ⁇ 10 7 9 ⁇ 10 7 3 ⁇ 10 6 5 ⁇ 10 10 resistivity ( ⁇ /sq.) Com- Com- Com- Com- Com- parative parative parative parative Example 1 Example 2 Example 3
  • Example 4 Example 5 Compound PP EPDM PS TPU PC (C) Mixture No.
  • An aluminum coating product of Comparative Example 4-8 was obtained in the same manner as Example 8 except that no mixtures were applied.
  • the surface resistivity of this coating product was 3.2 ⁇ 10 14 ⁇ cm.
  • a rubber sheet of Comparative Example 4-9 was obtained in the same manner as Example 9 except that as antistatic agent, 1 part by weight solution in which lithium bis(trifluoromethanesulfonyl)imide was dissolved at 5 percent by weight of polyethylene glycol (polymerization degree: 600, 20 percent of acetonitrile added) was used. Even though the volume resistivity of this rubber sheet was 2 ⁇ 10 9 ⁇ cm, bleeding-out was found to have occurred.
  • plasticizer 1 part by weight calcium stearate, 1 part by weight zinc stearate, 3 parts by weight epoxidized soybean oil, and 5.0 parts by weight mixture P-3 shown in Table 1 were blended with 100 parts by weight polyvinyl chloride with a polymerization degree of 1000.
  • a composition was obtained.
  • This composition was mixed at 160° C. for 5 minutes using mixing roll and subjected to press molding.
  • a transparent sheet of 1.0 mm thick was prepared.
  • the surface resistivity of this sheet was 5 ⁇ 10 7 ⁇ cm.
  • This sheet was heated at 190° C. for 30 minutes and the surface resistivity thereof was further measured, the value of which was 1 ⁇ 10 8 ⁇ cm.
  • the sheet remained transparent.
  • a sheet of Comparative Example 4-10 was obtained in the same manner as Example 4-10 except that as antistatic agent, 5.0 parts by weight lithium bis(trifluoromethanesulfonyl)imide was added.
  • the surface resistivity of this coating substance was 5 ⁇ 10 11 ⁇ cm.
  • This sheet was heated at 190° C. for 30 minutes and the surface resistivity thereof was further measured, the value of which was 9 ⁇ 10 11 ⁇ cm. The sheet changed its color to dark brown.
  • a cured-resin-composition molding was obtained in the same manner as Example 4-11 except that the composition P-7 shown in Table 1 was not added.
  • the volume resistivity of this cured-resin-composition molding was 4 ⁇ 10 13 ⁇ cm.
  • the antistatic composition according to the present invention provides a molding that is excellent in electric resistivity and is capable of exhibiting high antistatic properties over a long period of time.
  • metal salt such as lithium perchlorate and sodium perchlorate is contained in the composition of the present invention, when wrapping metal with a film or a sheet made of the composition, there is no corrosion, rust, or contamination on the metal surface.

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